Effect of silver on the photocatalytic degradation of humic acid

In this study, humic acid was mineralized and degraded photocatalytically in presence of bare TiO₂ and silver loaded TiO₂ (0.5–5.0 at.% Ag). X-ray diffraction (XRD) and inductive coupled plasma (ICP) analysis confirm the complete photodeposition of silver over TiO₂ by photodeposition method. X-ray photoemission spectroscopy (XPS) studies confirmed the presence of Ag⁰ in all Ag–TiO₂ samples and the absence of Ag⁺ ions. Silver loading over TiO₂ improved the rate of mineralization and degradation of humic acid with a maximum loading of 1.0 at.% Ag. Ninety percent carbon from humic acid was mineralized to CO₂ only after 60 min by using bare TiO₂ as a photocatalyst. However, this conversion was possible within 40 min by using 1.0 at.% Ag-loaded TiO₂. This observation verifies that coating of metals like silver over TiO₂ acts as an electron sink and can improve the redox reaction by preventing electron–hole recombination reaction. The optimum 1.0 at.% Ag loading in the current work is indicative that the blocking of the TiO₂ surface active sites by silver also plays an important role in the photocatalytic mineralization and degradation of humic acid. As the silver loading is increased, less number of active site are available over the surface of photocatalyst TiO₂ for redox reaction. This finding was supported by the TEM analysis of the photocatalyst samples.     

A comparative study of TiO2 supported noble metal catalysts for the oxidation of formaldehyde at room temperature

The TiO₂ supported noble metal (Au, Rh, Pd and Pt) catalysts were prepared by impregnation method and characterized by means of X-ray diffraction (XRD) and BET. These catalysts were tested for the catalytic oxidation of formaldehyde (HCHO). It was found that the order of activity was Pt/TiO₂  Rh/TiO₂ > Pd/TiO₂ > Au/TiO₂  TiO₂. HCHO could be completely oxidized into CO₂ and H₂O over Pt/TiO₂ in a gas hourly space velocity (GHSV) of 50,000 h⁻¹ even at room temperature. In contrast, the other catalysts were much less effective for HCHO oxidation at the same reaction conditions. HCHO conversion to CO₂ was only 20% over the Rh/TiO₂ at 20 °C. The Pd/TiO₂ and Au/TiO₂ showed no activities for HCHO oxidation at 20 °C. The different activities of the noble metals for HCHO oxidation were studied with respect to the behavior of adsorbed species on the catalysts surface at room temperature using in situ DRIFTS. The results show that the activities of the TiO₂ supported Pt, Rh, Pd and Au catalysts for HCHO oxidation are closely related to their capacities for the formation of formate species and the formate decomposition into CO species. Based on in situ DRIFTS studies, a simplified reaction scheme of HCHO oxidation was also proposed.     

Study of special cases where the enhanced photocatalytic activities of Pt/TiO2 vanish under low light intensity

Surface platinized TiO₂ (Pt/TiO₂) has been widely used and investigated but their properties are yet to be understood fully. Although it is known that the Pt effects depend on many experimental parameters and the kind of substrates, this study newly finds that the Pt effects could be also influenced by the light intensity. As for the photocatalytic degradation of trichloroethylene (TCE), the Pt effect was positive at high light intensity but was negative at low light intensity. A similar behavior was also observed in the photocurrent collection in the Pt/TiO₂ suspension with polyoxometalate (POM: PW₁₂O₄₀³⁻) used as an electron shuttle. The photocurrent collection in the Pt/TiO₂ suspension was less efficient than in TiO₂ suspension when the light intensity was low. Such abnormal light intensity-dependent behaviors were not observed in the photocatalytic degradation of dichloroacetate on Pt/TiO₂ and the Fe³⁺-mediated photocurrent collection in the Pt/TiO₂ suspension. It is proposed that the photochemical interactions between the Pt surface and reactive intermediates (TCE radical anions and reduced POM anions) induce a null reaction favorably at low light intensity condition.     

Photocatalytic reduction of carbon dioxide in aqueous semiconductor suspensions

Reactions of photocatalytic reduction of carbon dioxide in aqueous CdS, SiC, TiO₂, and SrTiO₃ suspensions with supported catalytic additives of Pt, Rh, Ru, Ag and Cu have been studied. In the absence of specially added electron donors, the carbon dioxide photoreduction is observed on the TiO₂ and SrTiO₃ suspensions only, those with CdS and SiC being inactive. The ratio of the reaction products (CO, C, methane) is dependent on the nature of the metal-catalyst on the semiconductor surface.     

Role of Cu in the Cu-TiO2 photocatalytic degradation of dihydroxybenzenes

The photocatalytic degradation of three dihydroxybenzenes (hydroquinone, catechol and resorcinol) by TiO₂ and Cu-TiO₂ has been studied. Degradation rates depend on the molecule catalyst surface interaction type. FTIR studies have shown that Cu presence modifies the organics interactions with the catalysts surface. Therefore, catalysts have shown different types of behaviour with each compound.

Resorcinol interaction with Cu-TiO₂ may produce a hydroxyphenolate thus reducing the number of activating centres in the aromatic ring. However, catechol interaction provides a catecholate bidentate which virtually deactivates the aromatic ring, hence reducing its degradation by OH radicals attacks. Hydroquinone interaction with Cu-TiO₂ occurs by means of a hydrogen bond, while with TiO₂ this interaction is established through the formation of a hydroxyphenolate monodentate. This justifies the improved catalytic behaviour of Cu-TiO₂.

Studies in presence of H₂O₂ have shown the existence of similar degradation mechanisms, but degradation rates have been notably higher.     

Phototransformation of metobromuron in the presence of TiO2

The photocatalytic degradation of the herbicide metobromuron was studied, using TiO₂ photocatalysts (Degussa P25 and Millennium PC50, PC100, PC105 and PC500). Intermediate products were identified by means of liquid chromatography–mass spectrometry (LC–MS–MS) using electrospray (ES) interfacing technique. In order of importance, the main reaction pathways were demethoxylation of the urea chain, ring oxidation leading to ortho hydroxylation with respect to the N atom, substitution of Br by OH, ring oxidation with formation of the meta hydroxylated compound. Demethylation of the demethoxylated product occurred as a secondary reaction. Formation of bromide ions was observed too. In the presence of 2-propanol used as a hydroxyl radical scavenger, demethoxylation was drastically inhibited while the other reactions were only partly inhibited. It suggests that demethoxylation was exclusively due to the oxidation by hydroxyl radicals, whereas the other reactions involved positive holes too. The degradation rate of metobromuron varied in the order: PC50 < PC100 < PC105 < PC500 < Degussa P25. TiO₂ Degussa P25 was therefore the most efficient photocatalyst although its surface area was lower than that of most of Millennium TiO₂.     

Photocatalytic degradation of organic compounds diluted in water using visible light-responsive metal ion-implanted TiO2 catalysts: Fe ion-implanted TiO2

The application of metal ion-implantation method has been made to improve the electronic properties of the TiO₂ photocatalyst to realize the utilization of visible light. The photocatalytic properties of these unique TiO₂ photocatalysts for the purification of water have been investigated. By the metal ion-implantation method, metal ions (Fe⁺, Mn⁺, V⁺, etc.) are accelerated enough to have the high kinetic energy (150 keV) and can be implanted into the bulk of TiO₂. TiO₂ photocatalysts which can absorb visible light and work as a photocatalyst efficiently under visible light irradiation were successfully prepared using this advanced technique. The UV-Vis absorption spectra of these metal ion-implanted TiO₂ photocatalysts were found to shift toward visible light regions depending on the amount and the kind of metal ions implanted. They were found to exhibit an effective photocatalytic reactivity for the liquid-phase degradation of 2-propanol diluted in water at 295 K under visible light (λ>450 nm) irradiation. The investigation using XAFS analysis suggested that the substitution of Ti ions in TiO₂ lattice with implanted metal ions is important to modify TiO₂ to be able to adsorb visible light.     

Effects of hydrothermal temperature and time on the photocatalytic activity and microstructures of bimodal mesoporous TiO2 powders

Bimodal nanocrystalline mesoporous TiO₂ powders with high photocatalytic activity were prepared by a hydrothermal method using tetrabutylorthotitanate (TiO(C₄H₉)₄, TBOT) as precursor. The as-prepared TiO₂ powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and N₂ adsorption–desorption measurements. The photocatalytic activity of the as-prepared TiO₂ powders was evaluated by the photocatalytic degradation of acetone (CH₃COCH₃) under UV-light irradiation at room temperature in air. The effects of hydrothermal temperature and time on the microstructures and photocatalytic activity of the TiO₂ powders were investigated and discussed. It was found that hydrothermal treatment enhanced the phase transformation of the TiO₂ powders from amorphous to anatase and crystallization of anatase. All TiO₂ powders after hydrothermal treatment showed bimodal pore-size distributions in the mesoporous region: one was intra-aggregated pores with maximum pore diameters of ca. 4–8 nm and the other with inter-aggregated pores with maximum pore diameters of ca. 45–50 nm. With increasing hydrothermal temperature and time, the average crystallite size and average pore size increased, in contrast, the Brunauer-Emmett-Teller (BET) specific surface areas, pore volumes and porosity steadily decreased. An optimal hydrothermal condition (180 °C for 10 h) was determined. The photocatalytic activity of the prepared TiO₂ powders under optimal hydrothermal conditions was more than three times higher than that of Degussa P25.     

Synthesis of functionalized mesoporous TiO2 molecular sieves and their application in photocatalysis

Functionalized mesoporous TiO₂ molecular sieves were prepared by treating ordered mesoporous TiO₂ with phosphoric acid or ammonium sulfate at high temperature. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption–desorption measurement, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectrometer (FT-IR). The photocatalytic activity of the samples was evaluated by photocatalytic decomposition of bromomethane (CH₃Br) in air. Results revealed that the functionalized TiO₂ samples preserved ordered mesostructure and exhibited enhanced physicochemical properties. The photocatalytic activity of the functionalized mesoporous TiO₂ sample was about three times higher than that of the pure mesoporous TiO₂. The concentrations of phosphoric acid and ammonium sulfate solutions used for the functionalization of TiO₂ greatly influenced the photocatalytic activity of the resultants materials. The optimal concentrations of phosphoric acid and ammonium sulfate solutions were 0.05 and 0.10 M, respectively. The enhanced photocatalytic performance of the functionalized mesoporous TiO₂ could be attributed to large specific surface area, high hydroxyl density, and enhanced surface chemical state.     

Photodegradation of benzothiazole ionic liquids catalyzed by titanium dioxide and silver-loaded titanium dioxide

In recent years, ionic liquids(ILs) have been widely used in extraction, synthesis, electrochemistry and other fields.Meanwhile, the environmental impact of ILs has been attracting a lot of attention, and eco-friendly treatment for ILs is becoming a necessary subject. In this study, photocatalytic degradations of benzothiazole ILs catalyzed by titanium dioxide(TiO_2) and silver-loaded titanium dioxide(Ag/TiO_2) were studied for the first time. The degradation of benzothiazole hexafluorophosphate([C4 Bth]PF6) could reach more than 99% within 240 min with the catalysis of TiO_2. To improve catalytic efficiency, Ag/TiO_2 was synthesized and characterized by UV–Vis diffuse reflectance absorption spectra(DRS) and X-ray photoelectron spectroscopy(XPS). The degradation of [C4 Bth]PF6 could reach more than 99% within 120 min in the degradation catalyzed by Ag/TiO_2. The photodegradation products of benzothiazole ILs are composed of inorganic substances or organic substances with simpler structures, which are easier to decompose and less toxic. The degradation system proposed by this study could provide a simple, green,safe, and economical method for the efficient treatment of benzothiazole ILs.     

Study of the synergic effect of sulphate pre-treatment and platinisation on the highly improved photocatalytic activity of TiO2

An important improvement of the photocatalytic activity of sol–gel prepared TiO₂ has been achieved by sulphate pre-treatment, calcination at high temperature and further platinisation of the samples.

The presence of sulphuric acid clearly stabilised TiO₂ surface area against sintering, maintaining at the same time anatase phase until higher calcination temperatures than in non-sulphated samples. Platinisation of the samples with different nominal amounts of platinum (from 0.5 to 2.5 wt%) was performed and the influence of sulphate treatment on the dispersion and deposit size of platinum on the TiO₂ surface was studied.

Characterisation results and photocatalytic activity of these catalysts were compared with those of unmodified TiO₂. Simultaneously sulphated and platinised TiO₂ samples were highly active for phenol degradation, used as model reaction for the photocatalytic studies, having higher activities than only platinised or only sulphated samples. The activity of these samples were several orders of magnitude higher than that of the commercial TiO₂ Degussa P25 (platinised or unmodified) as well, with independence of the nominal amount of platinum of the samples.

A wide characterisation of the samples was performed and correlations between characterisation results and activity properties are reported.     

Enhancement of photoinduced hydrogen production from irradiated Pt/TiO2 suspensions with simultaneous degradation of azo-dyes

The production of hydrogen from aqueous Pt/TiO₂ suspensions illuminated with UV–vis light has been examined in the absence and in presence of azo-dyes in solution. The effects of operational variables, including dye concentration, solution pH and temperature, on the rate of hydrogen production were investigated. It has been found that deposition of Pt (0.5 wt.%) on the semiconductor surface results in an increase of the H₂ production rate, which goes through a maximum with time of irradiation and then drops to steady-state values comparable to those obtained over bare TiO₂. Both, maximum and steady-state rates obtained over Pt/TiO₂ suspensions were found to increase with increasing solution pH and temperature. Addition of small quantities of azo-dyes in solution results in significantly enhanced rates of H₂ production for a period which depends on dye concentration, solution pH and, to a lesser extent, solution temperature. It is proposed that the dye acts as a scavenger of photogenerated oxidizing species while it is degraded toward CO₂ and inorganic ions. When complete mineralization is achieved, oxygen can no longer be removed from the photocatalyst surface and the rate drops to steady-state values, comparable to those obtained in the absence of azo-dye in solution. The amount of additional H₂ produced is directly proportional to the amount of dye added in the solution. The rate increases with increasing solution pH, where dye degradation is faster, indicating that the process is limited by the rate of consumption of photogenerated oxygen. It is concluded that, under certain experimental conditions, it is possible to obtain significantly enhanced rates of photoinduced hydrogen production from Pt/TiO₂ suspensions with simultaneous mineralization of azo-dyes. The process could be used for combined production of fuel H₂ and degradation of organic pollutants present in water.     

Structural peculiarities of TiO2 and Pt/TiO2 catalysts for the photocatalytic oxidation of aqueous solution of Acid Orange 7 Dye upon ultraviolet light

TiO₂ (anatase) with different microstructure was synthesized by thermal hydrolysis of the titanyl sulfate and studied by X-ray powder diffraction, high resolution transmission electron microscopy and UV–vis diffuse reflectance spectroscopy. The effect of titanium dioxide structure, regular or distorted, on the photocatalytic degradation of Acid Orange 7 Dye (AO7) in water upon ultraviolet light was studied. It was found that synthesized TiO₂ possesses a relatively high reactivity when illuminated but also show different adsorption in the dark. The relationship between these behaviors depends on the real structure of the catalysts. Catalysts with a perfect structural ordering formed after heating at temperature higher than 500 °C show better photocatalytic performance. Small amount of Pt added into the TiO₂ structure was found to improve further the catalyst reactivity. Pt-modified titania catalysts oxidize AO7 more efficiently than P-25 Degussa TiO₂. Doping effect of Pt on the structural and photocatalytic properties of the samples is discussed.     

Photocatalytic oxidation of methyl parathion over TiO2 and ZnO suspensions

The photocatalytic degradation of methyl parathion in aqueous solutions, using two different photocatalysts (TiO₂ and ZnO) has been investigated. The degradation of methyl parathion follows first order kinetics according to the Langmuir–Hinshelwood model. Complete degradation is achieved within 45 or 150 min when treated with illuminated TiO₂ or ZnO, respectively. It was observed that the initial rate increases linearly with an increase of the amount of catalyst up to a level where it reaches a plateau corresponding to the optimum of light absorption. The addition of an oxidant (K₂S₂O₈) leads to an increase in the rate of photooxidation. Moreover, illuminated TiO₂ suspensions were proved to be more effective in mineralizing the insecticide compared to ZnO suspensions. Measurements of phosphate, sulfate and nitrate ions gave valuable information about how this process is achieved. Addition of the oxidant enhances mineralization for both photocatalytic systems. Up to eight by-products were identified by GC–MS technique during the photocatalytic degradation of the insecticide that proceeds via oxidation, hydroxylation, dealkylation and hydrolysis of the ester group reaction pathways. Finally, the toxicity of the treated solution was reduced only in the presence of TiO₂, while ZnO suspensions appear to increase the toxicity due to photo-dissolution of ZnO releasing zinc in the treated solution.     

Relationship between the formation of surface species and catalyst deactivation during the gas-phase photocatalytic oxidation of toluene

Various partial oxidation products were identified on the surface of TiO₂ and an 8% SiO₂–TiO₂ binary catalyst used for the photocatalytic oxidation of gas-phase toluene. Using in situ FTIR spectroscopy, benzaldehyde and benzoic acid were identified on the surface of the deactivated photocatalysts. Additional GC/MS analysis of methanol-extracted surface species confirmed the presence of benzaldehyde and benzoic acid and detected small concentrations of benzyl alcohol. Apparently, benzaldehyde is the main partial oxidation product that is further oxidized to benzoic acid. Benzoic acid is strongly adsorbed on the surface of the catalyst. There seems to be a correlation between the accumulation of benzoic acid on the surface and catalyst deactivation. The presence of gas-phase water in the reactive mixture seems to retard the formation of benzoic acid.

The SiO₂–TiO₂ photocatalyst is more active and appears to deactivate slower than TiO₂. This binary oxide is photocatalytically active even in the absence of gas-phase oxygen. It also seems to have a higher toluene adsorption capacity than TiO₂. The acidity of the different oxides was examined using FTIR spectroscopy of adsorbed pyridine. The results indicate that no pure metal oxide displays Brønsted acidity but when SiO₂ is cofumed with TiO₂, Brønsted acidity of intermediate strength is generated. The generation of new surface sites may be responsible for the increased activity. The mechanism of this promotion effect is not clearly understood and further studies are required to elucidate it.     

C2H2 oxidation by plasma/TiO2 combination: Influence of the porosity, and photocatalytic mechanisms under plasma exposure

Plasma/catalyst combination is an active solution to reach high conversion rates at low energetic cost. TiO₂ is one of the catalysts frequently used in dielectric barrier discharges. Plasma/TiO₂ synergy was already exhibited but the mechanisms still have to be understood. This work distinguishes three main effects involved in the synergy: (a) effect of catalyst on the injected power, (b) the effect of porosity on C₂H₂ oxidation, and (c) the photocatalytic degradation of C₂H₂ on TiO₂ under plasma exposure. Different glass fibres-based catalytic materials coated with SiO₂ and/or TiO₂ nano-particles are used to separate these three contributions regarding to C₂H₂ conversion. It is reported that at constant voltage the injected power is mainly increased by the presence of glass fibres. C₂H₂ oxidation is mainly enhanced by the macroporosity of glass fibres and in a minor way by the nano-particles. The production of O atoms close to the surface is probably responsible for the higher C₂H₂ removal efficiency with porous material. The photocatalytic activity of TiO₂ is negligible in the plasma except if additional UV lamps are used to activate TiO₂. With external UV, photocatalytic activity is more efficient in the plasma phase than in a neutral gas phase. This plasma/photocatalysis synergy is due to the use of O atoms in photocatalytic mechanisms.     

Enhanced photocatalytic degradation of maleic acid by Fe(III) adsorption onto the TiO2 surface

The role of Fe(III) on the TiO₂-assisted photocatalytic degradation of maleic acid has been investigated. The study on the kinetics of the removal of organic matter, as well as the identification of all the stable mineralization intermediates, demonstrates that the presence of Fe(III), adsorbed onto the TiO₂ surface, renders a more efficient process through a cleaner mineralization pathway compared to bare TiO₂. Furthermore, the behaviour of the system does not depend on the iron source. On the other hand, the study of the Fe(III) influence on the interaction of maleic acid with TiO₂ in the solid phase, by means of ATR–FT-IR technique, has been performed. From all the reported results, it is concluded that the Fe(III) effects are mainly due to surface phenomena. The enhanced photocatalytic activity is interpreted under different perspectives, including adsorbed Fe–maleic complexes, enhanced adsorption of oxygen and lower geminate recombination yields.     

Photocatalytic treatment of wastewater from cottonseed processing: Effect of operating conditions, aerobic biodegradability and ecotoxicity

The heterogeneous and homogeneous UV-A photocatalytic treatment of an acidic waste stream originating from cottonseed processing was investigated. Several TiO₂ samples were screened in heterogeneous slurry experiments and a commercially available TiO₂ anatase (Millennium PC 500) was found to be considerably more active than the rest. The effect of key operating conditions such as effluent dilution (COD from 800 to 8000 mg/L), Millennium TiO₂ loading (from 100 to 1500 mg/L), solution pH (from 2.6 to 10) and the water matrix (presence of effluent solids and dissolved oxygen) on treatment efficiency was also studied. In general, degradation decreased with increasing effluent concentration, increasing solution pH from acidic to neutral and alkaline conditions and in the absence of oxygen serving as electron acceptor. Experiments with 500 mg/L TiO₂ for 240 min led to nearly complete mineralization at 800 mg/L initial COD but higher catalyst loadings suppressed degradation. Homogeneous experiments with 100 mg/L Fe²⁺ or Fe³⁺ were also performed leading to about 50% COD reduction; this increased to about 65% when H₂O₂ was added, i.e. simulating a Fenton reaction. The original, un-treated effluent was very toxic to marine bacteria Vibrio fischeri and very slowly biodegradable aerobically as assessed by shake-flask tests. Nonetheless, a 10-fold dilution (i.e. 800 mg/L COD) eliminated completely ecotoxicity and improved substantially biodegradation rates. On the other hand, photocatalytically pre-treated samples were less biodegradable than the un-treated one. Deep photocatalytic oxidation resulted in decreased ecotoxicity to V. fischeri, while moderate photocatalytic oxidation increased toxicity probably due to the formation of toxic intermediates.     

Optimisation of degradation conditions of 1,8-diazabicyclo[5.4.0]undec-7-ene in water and reaction kinetics analysis using a cocurrent downflow contactor photocatalytic reactor

The photocatalytic degradation of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, a non-biodegradable nitrogenous organic compound) in water was optimised under UV radiation using titanium dioxide photocatalyst. The reactor used was a pilot scale cocurrent downflow contactor photocatalytic reactor (CDCPR), a system offering very high mass transfer efficiency. The effect of photocatalyst loading, initial substrate concentration, temperature, pH, and different combinations of UV, O₂, H₂O₂ and TiO₂ on the photocatalytic oxidation of DBU was investigated. The TiO₂ photocatalyst used was Degussa VP Aeroperl P25/20, a granulated form of Degussa P-25, recently developed to ameliorate downstream catalyst separation problems. The CDCPR was fitted with an internally and vertically mounted 1.0 kW UV lamp. The reactions were carried out at 40–60 °C and 1 barg, with the reactor being operated in closed loop recycle mode and suspended photocatalyst being re-circulated. Optimisation of reaction conditions using a combination of TiO₂, UV radiation and O₂ gave the most rapid degradation and mineralisation of the DBU in comparison with other processes. Under optimised conditions, 100% degradation of DBU was achieved in 45 min, with a quantum yield of 7.39, using a 1 kW lamp, 0.5 g/dm³ TiO₂, 100 mg/dm³ DBU, 1 barg, 50 °C and pH of 3.17. Investigating the reaction pathway and its modelling showed a first order dependency, incorporating the effect of first intermediates of degradation. The activation energy was found to be 54.68 kJ mol⁻¹ showing a significant influence of temperature on the photocatalytic degradation of DBU.     

Photo-catalytic production of hydrogen form ethanol over M/TiO2 catalysts (M = Pd, Pt or Rh)

The photo-catalytic production of hydrogen from liquid ethanol, a renewable bio-fuel, over Rh/TiO₂, Pd/TiO₂ and Pt/TiO₂, anatase, has been studied. In the absence of the metal, TiO₂ shows negligible production of molecular hydrogen. The addition of Pd or Pt dramatically increases the production of hydrogen and a quantum yield of about 10% is reached at 350 K. On the contrary, the Rh doped TiO₂ is far less active. The low activity of Rh compared to that of Pd and Pt is not due to poor dispersion or low available Rh sites on the surface, as analyzed by XPS and TEM. For all three catalysts, TEM shows most particles with a size less than 10 nm. XPS results show that while the state of Pd and Pt particles in the as-prepared catalysts was mostly metallic that of the Rh was composed of non-negligible contribution of Rh cations. The extent of reaction of a series of alcohols was also studied, for comparison, on Pt/TiO₂. It was found that the reaction is governed by the solvation of the alcohol. In that regard, the production of molecular hydrogen over Pt/TiO₂ showed the following trend: methanol ≈ ethanol > propanol ≈ isopropanol > n-butanol.